WO2018097266A1 - 粘着シート及びその剥離方法 - Google Patents
粘着シート及びその剥離方法 Download PDFInfo
- Publication number
- WO2018097266A1 WO2018097266A1 PCT/JP2017/042290 JP2017042290W WO2018097266A1 WO 2018097266 A1 WO2018097266 A1 WO 2018097266A1 JP 2017042290 W JP2017042290 W JP 2017042290W WO 2018097266 A1 WO2018097266 A1 WO 2018097266A1
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- Prior art keywords
- pressure
- sensitive adhesive
- soluble
- adhesive layer
- adhesive sheet
- Prior art date
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68345—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used as a support during the manufacture of self supporting substrates
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68359—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used as a support during manufacture of interconnect decals or build up layers
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- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68372—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to support a device or wafer when forming electrical connections thereto
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- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
- H01L2221/68386—Separation by peeling
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/18—High density interconnect [HDI] connectors; Manufacturing methods related thereto
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
- H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet and a peeling method thereof.
- Adhesive sheets are widely used for applications such as bonding of articles and temporary fixing.
- the pressure-sensitive adhesive sheet generally has a configuration including a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive on a base material sheet.
- the adhesive sheet has an "adhesive adhesive sheet” used to adhere the substrate sheet itself to the adherend via the adhesive layer, and the adhesive layer is transferred to the adherend or the second substrate sheet.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2010-174148 discloses an adhesive layer in which dot-like adhesives are intermittently disposed on a substrate for the purpose of fixing paper such as envelopes. An adhesive product provided is disclosed. In this document, it is proposed to use an acrylic pressure-sensitive adhesive containing an acrylic copolymer in order to accurately and efficiently print an adhesive layer on a substrate by screen printing or gravure printing.
- Patent Document 2 Japanese Patent Application Laid-Open No.
- a transfer-type pressure-sensitive adhesive sheet material having a pressure-sensitive adhesive layer is disclosed, and acrylic, rubber-based, and silicone-based pressure-sensitive adhesives are exemplified.
- an adhesive sheet may be used for improving the handleability of a thin printed wiring board.
- Patent Document 3 Japanese Patent Laid-Open No. 2014-7315
- a heat-resistant film having a self-adhesive elastomer layer on a heat-resistant support layer is adhered to a printed wiring board, semiconductor chip mounting, reflow treatment, resin sealing,
- a semiconductor package manufacturing method including peeling a heat-resistant film after undergoing a curing treatment or the like is disclosed.
- This document also proposes forming the self-adhesive elastomer layer in a substantially dot shape or a substantially stripe shape.
- the adhesive layer is made of a material whose adhesive strength is lowered by heating or ultraviolet irradiation, and the sheet is easily peeled by losing the adhesive strength by heating or ultraviolet irradiation at the time of peeling.
- the applicable substrate sheet or adherend is limited to one that can transmit ultraviolet rays.
- the adhesive force of the adhesive layer is unintentionally lowered due to heat or ultraviolet irradiation received before the peeling step, and the necessary adhesion cannot be maintained.
- thermoplastic resin constituting the shell of the capsule is softened by heating, and the capsule expands and foams to form a microballoon. Adhesive strength decreases.
- this thermally expandable microcapsule cannot withstand a heating process such as solder reflow (eg, 260 ° C. or higher).
- the present inventors have recently adopted a soluble adhesive layer as the adhesive layer, and configured the soluble adhesive layer with an island-shaped or stripe-shaped pattern having a predetermined size, so that the adhesive strength of the adhesive layer is maintained until immediately before peeling. Obtained knowledge that it is possible to provide a pressure-sensitive adhesive sheet that can be easily peeled off from the adherend at an arbitrary timing while holding, and in a form that does not apply excessive stress to the adherend. .
- the object of the present invention is to easily remove the sheet from the adherend at an arbitrary timing while maintaining the adhesive strength of the adhesive layer until immediately before peeling, and without applying excessive stress to the adherend. It is in providing the adhesive sheet which can be performed.
- a pressure-sensitive adhesive sheet comprising a base material sheet and a soluble pressure-sensitive adhesive layer provided in an island-like or striped pattern on at least one surface of the base material sheet,
- the diameter of the circumscribed circle of each adhesive region constituting the island-shaped pattern is 0.1 mm or more and 10 mm or less
- the pattern is stripe-shaped
- an adhesive sheet in which the stripe width of each adhesive region constituting the stripe pattern is 0.1 mm or more and 10 mm or less.
- the pressure-sensitive adhesive sheet or the substrate sheet is peeled off from an adherend to which the pressure-sensitive adhesive sheet is attached, Injecting an alcohol-containing solution capable of dissolving the soluble adhesive layer into gaps between island-like or striped patterns of the soluble adhesive layer, and dissolving or softening the soluble adhesive layer; In a state where the soluble adhesive layer is dissolved or softened, and peeling the adhesive sheet or the substrate sheet from the adherend;
- FIG. 1 It is a cross-sectional schematic diagram which shows the one aspect
- PCD pitch circle diameter
- the pressure-sensitive adhesive sheet 10 of the present invention includes a base material sheet 12 and a soluble pressure-sensitive adhesive layer 14 on at least one surface of the base material sheet 12.
- the soluble adhesive layer 14 is provided in an island or stripe pattern.
- the pattern is island-shaped, the diameter of the circumscribed circle of each adhesive region 14a constituting the island-shaped pattern is 0.1 to 10 mm.
- the pattern is a stripe, the stripe width of each adhesive region 14a constituting the stripe pattern is 0.1 to 10 mm.
- the numerical range referred to by the expression “A to B” means A or more and B or less.
- the adhesive force of the soluble adhesive layer 14 is maintained until immediately before peeling by adopting the soluble adhesive layer 14 as the adhesive layer and configuring the soluble adhesive layer 14 with an island-like or striped pattern having a predetermined size.
- the soluble pressure-sensitive adhesive layer 14 is employed, so that the soluble pressure-sensitive adhesive layer 14 is dissolved or softened by immersing the soluble pressure-sensitive adhesive layer 14 in a soluble liquid (hereinafter referred to as a peeling solution).
- a peeling solution a soluble liquid
- the soluble adhesive layer 14 in an island-like or striped pattern having a predetermined size, it is possible to efficiently infiltrate the stripping solution (for example, an alcohol-containing solution) to every corner of the soluble adhesive layer 14.
- the stripping solution for example, an alcohol-containing solution
- the peeling liquid L is soluble. This is considered to be due to effective penetration into the gaps in the pattern of the adhesive layer 14 and promotion of contact with the individual adhesive regions 14a. As a result, it is possible to easily peel the sheet from the adherend 20.
- seat from the to-be-adhered body 20 may be what peels automatically by melt
- the adhesive layer may be made of a material whose adhesive strength is reduced by heating or ultraviolet irradiation, and a method of making the sheet easier to peel off by heating or ultraviolet irradiation at the time of peeling is also considered.
- the adhesive force of the adhesive layer is unintentionally lowered due to heat received before the process or irradiation of ultraviolet rays, and the necessary adhesion cannot be maintained.
- the pressure-sensitive adhesive sheet 10 of the present invention efficiently adheres the stripping solution to every corner of the soluble pressure-sensitive adhesive layer 14 provided in an island-like or stripe-like pattern having a predetermined size. This can be done without excessive stress on the body.
- the adhesive force of the soluble adhesive layer 14 can be maintained until immediately before the peeling, that is, the adhesive force of the adhesive layer before the peeling step. It is possible to avoid peeling due to decrease in the thickness. Therefore, the sheet can be peeled from the adherend at an arbitrary timing while maintaining the adhesive force of the pressure-sensitive adhesive layer until immediately before peeling.
- the build-up layer may be locally greatly curved when the substrate is peeled off from the substrate of the laminate produced using a coreless buildup method or the like.
- Such a large curvature of the build-up layer may cause disconnection or peeling of the wiring layer inside the build-up layer, and as a result, the connection reliability of the wiring layer may be reduced.
- the laminated body can be reinforced so as not to be bent locally, thereby improving the connection reliability of the laminated body and the flatness (coplanarity) of the laminated body surface.
- the present invention there is an advantage that peeling of the reinforcing sheet adhered to the laminate by the soluble adhesive layer 14 can be performed efficiently without applying excessive stress to the laminate.
- the pressure-sensitive adhesive sheet 10 may be either an adhesive-type pressure-sensitive adhesive sheet or a transfer-type pressure-sensitive adhesive sheet. Therefore, the pressure-sensitive adhesive sheet 10 may be one in which the pressure-sensitive adhesive sheet 10 itself is attached to an adherend and the base sheet 12 itself exhibits a desired function (for example, a protective function or a reinforcing function), which will be described later. As shown in FIGS. 7A (c) and (d), it is used to transfer the soluble adhesive layer 14 to the second substrate sheet 12 ′ (for example, a protective sheet or a reinforcing sheet), and the original substrate after the transfer. The sheet 12 may be peeled off. In the latter case, the laminated sheet obtained by transferring the soluble adhesive layer 14 to the second base sheet 12 ′ obtained as described above is also included in the category of the adhesive sheet of the present invention as the second adhesive sheet 10 ′. Shall.
- the soluble adhesive layer 14 is provided on at least one surface of the substrate sheet 12 in an island-like or stripe-like pattern. In addition, you may provide the soluble adhesion layer 14 on both surfaces of the base material sheet 12.
- FIG. When the soluble adhesive layer 14 forms an island pattern, the diameter of the circumscribed circle of each adhesive region 14a is 0.1 to 10 mm, preferably 0.1 to 5.0 mm, more preferably 0.1. ⁇ 2.0 mm.
- the stripe width of each adhesive region 14a is 0.1 to 10 mm, preferably 0.1 to 5.0 mm, more preferably 0.1. ⁇ 2.0 mm.
- the penetration of the release liquid into the gaps in the pattern of the soluble adhesive layer 14 is promoted to dissolve and release, etc.
- the sheet can be easily peeled off from the adherend.
- the soluble adhesive layer 14 preferably has an island pattern.
- the island-shaped pattern means a shape in which each adhesive region 14a is surrounded by a non-adhesive region 14b where there is no soluble adhesive layer 14 present therearound.
- Specific shapes of the individual adhesive regions 14a constituting the island pattern include various shapes such as a polygon and a circle, and a straight outline like the star polygon shown in FIG. 4A is used. It may be an intricate polygon or an irregular shape with a curved outline as shown in FIG. 4B.
- the island-shaped pattern is preferably a dot pattern, and the shape of each dot is typically a circle, but may be a shape close to a circle.
- the dot diameter defined as the diameter of the circumscribed circle of the individual dots constituting the dot pattern is preferably 10 mm or less, more preferably 0.1 to 5.0 mm, and still more preferably 0.1 to 2.0 mm. It is. As a result, the surface area of the soluble adhesive layer 14 is increased and the solubility is improved. As a result, the peelability is improved.
- the pitch circle diameter (PCD) of the dot pattern is preferably 0.45 to 3.0 mm, more preferably 0.6 to 2.4 mm, and still more preferably 0.8 to 2.0 mm.
- the pitch circle diameter (PCD) of the dot pattern means a virtual circle (pitch circle) formed by connecting the centers of the three closest dots in the dot pattern, as shown in FIG. (PC)) diameter (Pitch Circle Diameter).
- the soluble adhesive layer 14 preferably has a thickness of 0.5 to 50 ⁇ m, more preferably 1.0 ⁇ m or more and less than 30 ⁇ m, still more preferably 1.0 to 20 ⁇ m, particularly preferably 2.0 to 15 ⁇ m, most preferably 3.0 to 10 ⁇ m.
- the release liquid quickly penetrates into the gaps between the patterns of the soluble adhesive layer 14, so that the peelability of the adhesive sheet 10 is improved, and at the same time, the adherend having an island or stripe pattern is obtained. Indentation can be reduced.
- chip mounting, solder reflow, and compression molding are performed after sticking an adhesive sheet in semiconductor package manufacturing to reinforce the printed wiring board, indentations resulting from the adhesive region 14a remain on the printed wiring board.
- the thickness of the soluble pressure-sensitive adhesive layer 14 is 7.0 ⁇ m or less, there is an advantage that indentations hardly remain on the printed wiring board after compression molding.
- the soluble pressure-sensitive adhesive layer 14 has a dot pattern, if the dot diameter is 0.7 mm or less and the thickness of the soluble pressure-sensitive adhesive layer 14 is 1.0 to 7.0 ⁇ m, the indentation can be reduced and peeled off. It is particularly preferable since both of the properties can be realized more effectively.
- the distance between the centers of the circumscribed circles of the adhesive region 14a is preferably larger than the average value of the diameters of the circumscribed circles from the viewpoint that a sufficient gap can be secured between the individual adhesive regions 14a.
- the distance between the centers of the circumscribed circles of the adhesive region is preferably 0.1 to 20 mm, more preferably 0.2 to 10 mm, still more preferably 0.3 to 5.0 mm, particularly preferably. 0.4 to 2.0 mm.
- the island-like pattern may be composed of one or a plurality of clusters that provide a polygonal, circular, annular, belt-like, or lattice-like pattern as a whole, each of which has three or more adhesive regions. It can be composed of a collection of That is, the island-like pattern (for example, dot pattern) is formed not only in a mode that is uniformly provided over the entire surface of the base sheet 12 as shown in FIG. 6A but also in an aggregate of three or more adhesive regions 14a.
- the one or more clusters 18 that are formed are generally polygonal (eg, a square as shown in FIG. 6B), a circle as shown in FIG. 6C, an annulus as shown in FIG. 6D, and shown in FIG. 6E.
- the ratio of the adhesive region 14a to the total area of the surface of the base sheet 12 on which the soluble adhesive layer 14 is provided is preferably 3 to 90% by area, more preferably 3 to 75% by area, and still more preferably 5%. It is ⁇ 60 area%, particularly preferably 5 to 40 area%.
- “the total area of the surface of the base sheet 12 on which the soluble adhesive layer 14 is provided” means that the base sheet is formed when the soluble adhesive layer 14 is provided on one side of the base sheet 12. 12 means the total area of the surface adjacent to the soluble adhesive layer 14, and when the soluble adhesive layer 14 is provided on both surfaces of the substrate sheet 12, it means the total area of both surfaces of the substrate sheet 12. .
- the proportion of the adhesive region 14a is within the above range, the penetration of the stripping solution into the pattern gap of the soluble adhesive layer 14 is promoted while sufficiently securing the adhesive force by the soluble adhesive layer 14 before the stripping solution enters.
- the sheet can be more easily peeled off from the adherend.
- this is not the case in applications where it is sufficient to have a minimum adhesive strength in the process for the purpose of simple fixation.
- the soluble adhesive layer 14 is a layer that can be dissolved or softened in contact with the stripping solution as well as exhibiting adhesiveness at room temperature. Therefore, the soluble adhesive layer 14 preferably contains a solution-soluble resin, for example, an acid-soluble resin or an alkali-soluble resin. Since this solution-soluble resin can be efficiently dissolved or softened by contact with the stripping solution, the sheet can be peeled from the adherend more effectively.
- a solution-soluble resin for example, an acid-soluble resin or an alkali-soluble resin. Since this solution-soluble resin can be efficiently dissolved or softened by contact with the stripping solution, the sheet can be peeled from the adherend more effectively.
- a preferred solution-soluble resin is an alkali-soluble resin. This is because the soluble adhesive layer 14 may not substantially dissolve in a neutral or acidic solution, assuming application of an article that can come into contact with a neutral or acidic solution such as a printed wiring board. This is because it is desired. For example, when application of the soluble adhesive layer 14 to a printed wiring board is considered, when a resin (for example, a water-soluble resin) that dissolves in a neutral solution is used as the soluble adhesive layer 14, water washing in the manufacturing process of the printed wiring board is performed. The resin may be dissolved in the process, or the resin may be altered by absorption of moisture in the atmosphere.
- a resin for example, a water-soluble resin
- the alkali-soluble resin particularly preferably contains a polymer containing at least one of a carboxyl group and a phenolic hydroxyl group. Since such a polymer is particularly easily dissolved in an alkaline solution, the dissolution of the soluble adhesive layer 14 is promoted, and the sheet can be peeled from the adherend in a shorter time.
- the polymer containing at least one of a carboxyl group and a phenolic hydroxyl group include an acrylic resin containing a carboxyl group and a phenol novolac resin containing a phenolic hydroxyl group.
- the acrylic resin-based adhesive is a copolymer of an acrylic monomer (for example, acrylic acid or methacrylic acid) having a carboxyl group and an unsaturated double bond in the molecule, and ethyl acrylate or butyl acrylate. Can be synthesized.
- the adhesive force of the soluble adhesive layer 14 and the solubility in an alkaline solution can be controlled by adjusting the type and ratio of the acrylic monomer.
- the adhesive strength of the soluble adhesive layer 14 and the solubility control in an alkaline solution can also be controlled by adding a resin (for example, an epoxy resin) that causes a crosslinking reaction of a carboxyl group to an acrylic resin containing a carboxyl group. Can do.
- the alkaline solution used as the stripping solution is preferably a sodium hydroxide solution and / or a potassium hydroxide solution.
- the preferred concentration of these solutions is 0.5 to 50% by weight. Within this range, the alkalinity is increased, the dissolving power is improved, and sodium hydroxide and / or potassium hydroxide is less likely to precipitate even when the room temperature when using the stripping solution is low.
- an organic solvent for example, 2-propanol capable of dissolving the acrylic resin and / or novolac resin may be added to the alkaline solution.
- a preferable addition amount of the organic solvent is 5 to 50% by weight with respect to 100% by weight of the alkaline solution. If it is within this range, the volatilization amount during the work is reduced while desirably realizing a shortening of the dissolution time, so that it becomes easy to manage the concentration of the alkaline substance and the safety is also improved.
- a preferred organic solvent is an alcohol, and preferred examples of the alcohol include 2-propanol, methanol, ethanol, and 2-butanol.
- An appropriate amount of surfactant may be added to the alkaline solution. Since the penetration and wettability of the solution with respect to the resin are improved by the addition of the surfactant, the dissolution time of the soluble adhesive layer 14 can be further shortened.
- the kind of surfactant is not specifically limited, What kind of thing may be sufficient.
- any of anionic, cationic and nonionic surfactants can be used.
- the form of the base sheet 12 is not limited to what is generally referred to as a sheet, but may be other forms such as a film, a plate, and a foil.
- the base sheet 12 may be a laminate of these sheets, films, plates, foils, and the like.
- polishing treatment, release agent application, Surface treatment may be performed in advance by a known method such as plasma treatment.
- the base sheet 12 is preferably composed of at least one resin of polyethylene terephthalate (PET) and polyethylene (PE), more preferably polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- PET polyethylene
- PET polyethylene
- the base sheet 12 transfers the soluble pressure-sensitive adhesive layer 14 to the adherend or the second base sheet prepared separately and the function of holding the soluble pressure-sensitive adhesive layer 14.
- the base sheet 12 of this embodiment is suitable for such use.
- the substrate sheet 12 preferably has a thickness of 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, still more preferably 25 to 75 ⁇ m.
- the substrate sheet 12 is selected from the group consisting of metal (preferably metal plate or metal foil), glass, glass epoxy resin, polyimide resin, and phenol resin (bakelite). It is preferable to be composed of at least one kind.
- the base sheet 12 is preferably made of a phenolic resin (bakelite) from the viewpoint of cost.
- the base sheet 12 is based on strength.
- the material sheet 12 is preferably made of metal. Since these materials all have heat resistance, deterioration in the heat treatment process can be prevented.
- the base material sheet 12 prevents the curved printed circuit board from being handled and improved in the semiconductor package manufacturing process in addition to the function of holding the soluble pressure-sensitive adhesive layer 14.
- the base sheet 12 of this embodiment is suitable for such applications.
- the preferred thickness of the base sheet 12 when used as an adhesive pressure-sensitive adhesive sheet is preferably 10 ⁇ m to 1 mm, more preferably from the viewpoint of maintaining strength of the base sheet 12 and ease of handling of the base sheet 12.
- the thickness is 50 to 800 ⁇ m, more preferably 100 to 600 ⁇ m.
- the substrate sheet 12 When the pressure-sensitive adhesive sheet 10 is used as an adhesive-type pressure-sensitive adhesive sheet, the substrate sheet 12 preferably has a Vickers hardness lower than that of an adherend (for example, a printed wiring board). Thereby, when laminating or peeling the pressure sensitive adhesive sheet 10 on an adherend (for example, a printed wiring board), the base sheet 12 itself bends, so that stress that can occur at the time of lamination or peeling can be released well. As a result, it is possible to effectively prevent or suppress the bending of the adherend (for example, a printed wiring board).
- the Vickers hardness of the substrate sheet 12 is preferably 2 to 99%, more preferably 6 to 90%, and still more preferably 10 to 85% of the Vickers hardness of the adherend (for example, printed wiring board).
- the substrate sheet 12 preferably has a Vickers hardness of 50 to 700 HV, more preferably 150 to 550 HV, and still more preferably 170 to 500 HV.
- the Vickers hardness is measured in accordance with the “Vickers hardness test” described in JIS Z 2244-2009.
- Vickers hardness HV of various materials is exemplified below: sapphire glass (2300 HV), cemented carbide (1700 HV), cermet (1650 HV), quartz (crystal) (1103 HV), SKH56 (high speed tool) Steel, high speed steel (722HV), tempered glass (640HV), SUS440C (stainless steel) (615HV), SUS630 (stainless steel) (375HV), titanium alloy 60 (64 alloy) (around 280HV), Inconel (heat resistant nickel) Alloy) (150 to 280HV), S45C (carbon steel for machine structure) (201 to 269HV), Hastelloy alloy (corrosion resistant nickel alloy) (100 to 230HV), SUS304 (stainless steel) (187HV), SUS430 (stainless steel) ( 183HV), cast iron 160 ⁇ 180 Hv), titanium alloy (110 ⁇ 150HV), brass (80 ⁇ 150HV), and bronze (50 ⁇ 100H
- the base sheet 12 has a spring limit value Kb 0.1 of 100 to 1500 N / mm 2 measured according to the JIS H 3130-2012 repeated bending test. More preferably, it is 150 to 1200 N / mm 2 , more preferably 200 to 1000 N / mm 2 .
- Kb spring limit value
- the base sheet 12 itself bends, so that stress that may occur at the time of lamination or peeling is generated. As a result, it is possible to prevent or suppress the bending of the adherend (for example, a printed wiring board) more effectively.
- the base material sheet 12 bent at the time of lamination or peeling can be instantaneously returned to its original flat shape by utilizing its elasticity, the flatness (coplanarity) of the adherend (for example, a printed wiring board). Can be effectively maintained.
- the base sheet 12 to which the peeling force is applied is biased in the peeling direction (that is, the direction away from the adherend (for example, printed wiring board)). As a result, smoother peeling becomes possible.
- the substrate sheet 12 preferably has a through hole in the thickness direction.
- the adherend for example, a printed wiring board
- the peeling liquid can enter the gaps in the pattern of the soluble pressure-sensitive adhesive layer 14 through the through holes provided in the base material sheet 12. Therefore, the soluble adhesive layer 14 is more efficiently dissolved, and as a result, the peelability is further improved.
- the pressure-sensitive adhesive sheet 10 further includes a protective film 16 laminated on the soluble pressure-sensitive adhesive layer 14 in terms of easy handling.
- the material of the protective film 16 is not particularly limited, but is preferably made of resin.
- the resin constituting the protective film include polyethylene terephthalate (PET), polyethylene (PE), or a combination thereof, and polyethylene terephthalate (PET) is more preferable.
- the thickness of the protective film 16 is preferably 10 to 40 ⁇ m, more preferably 15 to 30 ⁇ m. Since the protective film 16 protects the soluble adhesive layer 14 until the adhesive sheet 10 is used, the protective film 16 is peeled off from the adhesive sheet 10 during use.
- the adhesive force (for example, peel strength) between the soluble adhesive layer 14 and the protective film 16 is preferably lower than the adhesive force (for example, peel strength) between the soluble adhesive layer 14 and the base sheet 12.
- the protective film 16 can be peeled preferentially over the base sheet 12, the protective film 16 can be more easily maintained while stably maintaining the close contact state between the base sheet 12 and the soluble adhesive layer 14. And it can be peeled off smoothly.
- the surface to which the soluble pressure-sensitive adhesive layer 14 of the protective film 16 is applied is subjected to polishing treatment, application of a release agent, plasma treatment, etc. Surface treatment may be performed in advance by a known method.
- the pressure-sensitive adhesive sheet 10 of the present invention can be applied to various adherends that require desired adhesiveness, and its use is not particularly limited. Most preferably, it is used for reinforcing printed wiring boards.
- 7A to 7C show a semiconductor package manufacturing process using the pressure-sensitive adhesive sheet 10 of the present invention. Note that the step shown in FIG. 7B may be performed following the step shown in FIG. 7A, or the step shown in FIG. 7C may be performed following the step shown in FIG. 7A.
- the adhesive sheet 10 provided in order with the base material sheet 12, the soluble adhesive layer 14, and the protective film 16 is prepared as a transfer type adhesive sheet (process (a)).
- the protective film 16 is peeled off (step (b)), and the soluble adhesive layer 14 is transferred to the second base sheet 12 ′ having a function as a reinforcing sheet by roll lamination (step (c)).
- the base sheet 12 is peeled off (step (d)).
- the second pressure-sensitive adhesive sheet 10 ′ composed of the second base sheet 12 ′ to which the soluble pressure-sensitive adhesive layer 14 is thus transferred is also included in the category of the pressure-sensitive adhesive sheet of the present invention as an adhesive pressure-sensitive adhesive sheet.
- 2nd adhesive sheet 10 ' is attached to the printed wiring board 20p by vacuum lamination (process (e)).
- the obtained laminate is subjected to solder paste printing on the printed wiring board 20p, and then immersed in an alkaline solution (step (i)) as shown in FIG. 7B (step (i)).
- Sheet) step (j)
- FIG. 7C mounting of semiconductor chip 22 (chip mounting) (step (f)), solder reflow (step (g)), and
- the substrate may be immersed in an alkaline solution (step (i)) to peel off the second base sheet 12 ′ (reinforcing sheet) (step (j)).
- step (h) in the step (h), the semiconductor chip 22 can be sealed with the insulating resin 24.
- the second base sheet 12 ′ functions as a reinforcing sheet, the connection reliability and surface flatness (coplanarity) of the printed wiring board 20p can be improved, and the process can be simplified and the yield can be improved. be able to.
- the adhesive force of the soluble adhesive layer 14 can be maintained until the peeling process, careless peeling that hinders handling does not occur.
- the second base sheet 12 ′ can be easily peeled from the printed wiring board 20p in a form that does not apply excessive stress to the printed wiring board 20p.
- Peeling method of pressure-sensitive adhesive sheet The pressure-sensitive adhesive sheet 10 of the present invention is used by being attached to some adherend 20. And peeling of the adhesive sheet 10 or the base material sheet 12 from the adherend 20 to which the adhesive sheet 10 is attached can be preferably performed by the following procedure.
- an alcohol-containing solution capable of dissolving the soluble adhesive layer 14 is allowed to enter the gaps between the island-shaped or striped patterns of the soluble adhesive layer 14 to dissolve or soften the soluble adhesive layer 14.
- the penetration of the alcohol-containing solution into the gap may be performed by bringing the entire adherend 20 to which the pressure-sensitive adhesive sheet 10 is attached into contact with the alcohol-containing solution, which is a stripping solution, by dipping or the like.
- the alcohol contained in the alcohol-containing solution capable of dissolving the soluble adhesive layer 14 include 2-propanol, methanol, ethanol, and 2-butanol, and most preferably have good solubility in water, and 2-Propanol from the viewpoint of obtaining good peelability.
- the alcohol concentration in the alcohol-containing solution is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, and still more preferably 20 to 50% by weight. Within such a range, the soluble adhesive layer 14 can be more effectively dissolved or softened, and the reduced alcohol concentration makes it difficult to ignite, improving safety.
- the alcohol-containing solution is preferably a solution containing a basic substance such as KOH, NaHCO 3 , Na 2 CO 3 , or NaOH, from the viewpoint of stabilization while controlling the peelability, and the basic substance in the alcohol-containing solution
- the preferred concentration is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1.0 to 15% by weight. Therefore, the alcohol-containing solution may include an alkaline solution as described above.
- the adhesive sheet 10 or the base sheet 12 is peeled from the adherend 20 in a state where the soluble adhesive layer 14 is dissolved or softened.
- the sheet from the adherend 20 may be peeled off automatically by dissolution of the soluble pressure-sensitive adhesive layer 14, or mechanically in a state where the adhesive force is significantly reduced by dissolution or softening of the soluble pressure-sensitive adhesive layer 14. It may be peeled off.
- a pressure-sensitive adhesive sheet 10 is prepared by preparing a soluble pressure-sensitive adhesive and printing the soluble pressure-sensitive adhesive in an island-like or striped pattern on the substrate sheet 12 to form a soluble pressure-sensitive adhesive layer 14. be able to. Since the pattern of the soluble adhesive layer 14 and the size and shape of the individual adhesive regions 14a are substantially equivalent to the design of the plate in printing, the desired soluble adhesive layer 14 is formed by appropriately changing the design of the plate. be able to.
- the printing method may be performed using a known method such as dot pattern printing, screen printing, gravure printing (intaglio printing), and is not particularly limited. It is preferable to use gravure printing from the viewpoint that printing in a roll-to-roll method is possible and mass productivity is high.
- Examples 1-3 Preparation of pressure-sensitive adhesive sheet 1% by weight of a curing agent (TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on a carboxyl group-containing acrylic resin (COPONIL TM , manufactured by Nippon Synthetic Chemical Industry Co., Ltd., N-2584)
- a soluble pressure-sensitive adhesive containing a polymer containing a carboxyl group was prepared. This soluble adhesive was subjected to gravure printing on a polyethylene terephthalate (PET) sheet with the predetermined dot pattern shown in Table 3 to obtain an adhesive sheet.
- PET polyethylene terephthalate
- This gravure printing is a plate engraved with a printed image of a dot pattern that meets the specifications shown in Table 3 (dot diameter (that is, the diameter of the circumscribed circle of each dot), pitch circle diameter (PCD) and adhesive area ratio) (Cylinder having a printing width of about 700 mm and a diameter of 200 mm) was used so that the total thickness of the base sheet and the soluble adhesive layer was 100 ⁇ m.
- 2nd base material sheet 12 ' (stainless steel plate) was affixed on the printed wiring board 20p via the soluble adhesion layer 14, and it was set as the evaluation laminated body 26 (process (e)).
- the evaluation laminate 26 was immersed in a stripping solution (10 wt% sodium hydroxide solution) in a state of standing (step (i)).
- the time (maximum 18 hours) required from the start of immersion until the second substrate sheet 12 ′ (stainless steel plate) peels from the printed wiring board 20p is measured (step (j)), and rating is evaluated according to the following criteria: did.
- the results were as shown in Table 3.
- -Evaluation AA The time from when the soluble adhesive layer was dissolved until the stainless steel plate was peeled off was within 30 minutes. That is, since the soluble adhesive layer dissolves very quickly, a significant improvement in productivity can be expected.
- -Evaluation A The time from the dissolution of the soluble adhesive layer to the peeling of the stainless steel plate was over 30 minutes and within 1 hour. That is, since the soluble adhesive layer dissolves quickly, an improvement in productivity can be expected.
- -Evaluation B The time from the dissolution of the soluble adhesive layer to the peeling of the stainless steel plate was over 1 hour and within 3 hours. This level of peelability is sufficient when there is no particular requirement for speeding up the process.
- -Evaluation C The stainless steel plate did not peel even after immersion for 18 hours.
- ⁇ Evaluation 2 Remaining indentation (after compression molding)>
- the remaining impression was evaluated after compression molding. That is, the evaluation laminated body 26 is produced in the same procedure as in evaluation 1 (steps (c) to (e)), and the semiconductor chip 22 is mounted on the printed wiring board 20p of the evaluation laminated body 26 (step (f) )), Solder reflow was performed (step (g)), and then compression molding (molding) was performed at 175 ° C. and 8 MPa (step (h)) to obtain a laminate 28 for evaluation of residual indentations.
- the laminate 28 for evaluation of residual indentation is left standing and immersed in a stripping solution (10% by weight sodium hydroxide solution) (step (i)), from the printed wiring board 20p to the second substrate sheet 12 ′ ( The stainless steel plate was peeled off (step (j)). Thereafter, the indentation remaining on the printed wiring board 20p was observed with a microscope, and rated according to the following criteria. The results were as shown in Table 3.
- -Evaluation A Indentation depth was less than 5 ⁇ m.
- -Evaluation B The indentation depth was 5 ⁇ m or more and 10 ⁇ m or less. This indentation depth does not affect the subsequent process, but the appearance is not good.
- -Unevaluable Since the stainless steel plate did not peel even after 18 hours of immersion, the indentation residue could not be evaluated.
- Example 4 (Comparison) A pressure-sensitive adhesive sheet was prepared and evaluated 1-1 and 2 in the same manner as in Example 1 except that a solid pressure-sensitive adhesive layer was formed using a plate (cylinder) on which a print image was not engraved. The results were as shown in Table 3.
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Abstract
Description
前記パターンが島状である場合には、該島状のパターンを構成する個々の粘着性領域の外接円の直径が0.1mm以上10mm以下であり、前記パターンがストライプ状である場合には、該ストライプ状のパターンを構成する個々の粘着性領域のストライプ幅が0.1mm以上10mm以下である、粘着シートが提供される。
前記可溶性粘着層を溶解可能なアルコール含有溶液を、前記可溶性粘着層の島状又はストライプ状のパターンの隙間に浸入させて、前記可溶性粘着層を溶解又は軟化させる工程と、
前記可溶性粘着層が溶解又は軟化された状態で、前記粘着シート又は前記基材シートを前記被着体から剥離する工程と、
を含む、方法が提供される。
本発明の粘着シートが図1及び2に模式的に示される。図1及び2に示されるように、本発明の粘着シート10は、基材シート12と、基材シート12の少なくとも一方の面に可溶性粘着層14を備える。可溶性粘着層14は、島状又はストライプ状のパターンで設けられる。上記パターンが島状である場合には、上記島状のパターンを構成する個々の粘着性領域14aの外接円の直径は0.1~10mmである。一方、上記パターンがストライプ状である場合には、上記ストライプ状のパターンを構成する個々の粘着性領域14aのストライプ幅は0.1~10mmである。なお、本明細書において「A~B」の表現で言及される数値範囲は、A以上B以下を意味するものとする。このように、粘着層として可溶性粘着層14を採用し、かつ、可溶性粘着層14を所定寸法の島状又はストライプ状のパターンで構成することで、剥離直前まで可溶性粘着層14の粘着力を保持しながら、被着体からのシートの剥離を任意のタイミングで、しかも被着体に過度の応力を与えない形で容易に行うことが可能となる。すなわち、本発明の粘着シート10では可溶性粘着層14を採用しているため、可溶性粘着層14を溶解可能な液体(以下、剥離液という)に浸漬することで、可溶性粘着層14を溶解又は軟化させることができる。しかも、可溶性粘着層14を所定寸法の島状又はストライプ状のパターンで構成することで、剥離液(例えばアルコール含有溶液)を可溶性粘着層14の隅々まで効率的に浸透させることができる。これは、図3に点線の矢印で模式的に示されるように、被着体20(例えばプリント配線板)に接着された可溶性粘着層14を剥離液Lに浸漬した際、剥離液Lが可溶性粘着層14のパターンの隙間に効果的に浸透して、個々の粘着性領域14aとの接触が促進されることによるものと考えられる。その結果、被着体20からのシートの剥離を容易に行うことが可能となる。なお、被着体20からのシートの剥離は、可溶性粘着層14の溶解によって自動的に剥がれるものであってもよいし、可溶性粘着層14の溶解又は軟化によって粘着力が有意に低下した状態で機械的に引き剥がすものであってもよい。
本発明の粘着シート10は、所望の粘着性を要する様々な被着体に適用することができ、その用途は特に限定されるものではないが、半導体パッケージ製造におけるプリント配線板の補強のために用いられるのが最も好ましい。図7A~Cに本発明の粘着シート10を用いた半導体パッケージの製造プロセスが示される。なお、図7Aに示される工程に続けて図7Bに示される工程が行われてもよいし、図7Aに示される工程に続けて図7Cに示される工程が行われてもよい。いずれにしても、図7Aに示されるプロセスでは、基材シート12、可溶性粘着層14及び保護フィルム16を順に備えた粘着シート10が転写型粘着シートとして準備される(工程(a))。次いで保護フィルム16が引き剥がされて(工程(b))、可溶性粘着層14がロールラミネーションにより、補強シートとしての機能を備えた第二の基材シート12’に転写され(工程(c))、基材シート12が引き剥がされる(工程(d))。こうして可溶性粘着層14が転写された第二の基材シート12’からなる第二の粘着シート10’も、接着型粘着シートとして本発明の粘着シートの範疇に含まれる。そして、第二の粘着シート10’が真空ラミネーションによりプリント配線板20pに取り付けられる(工程(e))。得られた積層体は、プリント配線板20pにはんだペースト印刷を施した後、図7Bに示されるように、アルカリ性溶液に浸漬して(工程(i))第二の基材シート12’(補強シート)を剥離してもよいし(工程(j))、図7Cに示されるように、半導体チップ22の実装(チップ実装)(工程(f))、はんだリフロー(工程(g))、及び圧縮成型(工程(h))を施した後、アルカリ性溶液に浸漬して(工程(i))、第二の基材シート12’(補強シート)を剥離してもよい(工程(j))。なお、図7Cに示されるように、工程(h)は半導体チップ22が絶縁樹脂24で封止されうる。いずれにしても、第二の基材シート12’が補強シートとして機能するため、プリント配線板20pの接続信頼性と表面の平坦性(コプラナリティ)を向上でき、工程簡略化や歩留向上を図ることができる。しかも、剥離工程に至るまでの間、可溶性粘着層14の粘着力を保持できるため、ハンドリングに支障を来たす不用意な剥離が生じない。そして、最後に、アルカリ性溶液に浸漬させることで、プリント配線板20pから第二の基材シート12’をプリント配線板20pに過度の応力を与えない形で容易に剥離することができる。
本発明の粘着シート10は何らかの被着体20に貼り付けられることにより使用されるものである。そして、粘着シート10が貼り付けられた被着体20からの粘着シート10又は基材シート12を剥離は次の手順で好ましく行うことができる。
可溶性粘着剤を用意し、この可溶性粘着剤を島状又はストライプ状のパターンで基材シート12上に印刷して可溶性粘着層14を形成することで、粘着シート10を作製することができる。可溶性粘着層14のパターン及び個々の粘着性領域14aの大きさや形状は印刷における版の設計とほぼ同等になることから、版の設計を適宜変更することで、所望の可溶性粘着層14を形成することができる。印刷手法は、ドットパターン印刷、スクリーン印刷、グラビア印刷(凹版印刷)等の公知の手法を用いて行えばよく、特に限定されるものではないが、安定した連続印刷が可能な点、及びロール・トゥ・ロール(Roll to Roll)方式での印刷が可能で量産性が高い点から、グラビア印刷を用いることが好ましい。
(1)粘着シートの作製
カルボキシル基含有アクリル系樹脂(コーポニールTM、日本合成化学工業株式会社製、N-2584)に、硬化剤(TETRAD-C、三菱ガス化学株式会社製)を1重量%添加して、カルボキシル基を含有するポリマーを含む可溶性粘着剤を調製した。この可溶性粘着剤をポリエチレンテレフタレート(PET)シートに、表3に示される所定のドットパターンでグラビア印刷して粘着シートを得た。このグラビア印刷は、表3に示される仕様(ドット径(すなわち個々のドットの外接円の直径)、ピッチ円直径(PCD)及び粘着性領域割合)を満たすドットパターンの印刷イメージが彫り込まれた版(印刷幅約700mm、直径200mmのシリンダー)を用いて、基材シートと可溶性粘着層との合計厚さが100μmになるように行った。
得られた粘着シートについて、以下の各種評価を行った。
図7A及び7Bに示される工程流れ図に準じてアルカリ性溶液における剥離性評価を行った。すなわち、粘着シート10の可溶性粘着層14が設けられた面に第二の基材シート12’としてステンレス鋼板を積層した(工程(c))、その後、この積層体から基材シート12を剥離した(工程(d))。こうして、粘着シート10の可溶性粘着層14を第二の基材シート12’であるステンレス鋼板に転写した。次に、可溶性粘着層14を介して第二の基材シート12’(ステンレス鋼板)をプリント配線板20pに貼り付けて評価用積層体26とした(工程(e))。評価用積層体26を静置した状態で剥離液(10重量%水酸化ナトリウム溶液)に浸漬させた(工程(i))。浸漬開始から、プリント配線板20pから第二の基材シート12’(ステンレス鋼板)が剥離するまでに要した時間(最大18時間)を測定し(工程(j))、以下の基準で格付け評価した。結果は表3に示されるとおりであった。
‐評価AA:可溶性粘着層が溶解してステンレス鋼板が剥離するまでの時間が30分以内であった。すなわち、可溶性粘着層が極めて早く溶解するため、生産性の大幅な向上が期待できる。
‐評価A:可溶性粘着層が溶解してステンレス鋼板が剥離するまでの時間が30分を超え1時間以内であった。すなわち、可溶性粘着層が早く溶解するため、生産性の向上が期待できる。
‐評価B:可溶性粘着層が溶解してステンレス鋼板が剥離するまでの時間が1時間を超え3時間以内であった。プロセス高速化の要求が特に無い場合はこの程度の剥離性でも十分である。
‐評価C:18時間浸漬後においてもステンレス鋼板が剥離しなかった。
例2についてのみ、剥離液として、アルカリ性溶液の代わりに、1.5重量%水酸化カリウム及び25重量%2-プロパノールの混合液(すなわちアルコール含有溶液)を用いたこと以外は、評価1-1と同様にして剥離性評価を行った。結果は表3に示されるとおりであった。
図7A及び7Cに示される工程流れ図に準じて圧縮成型後の圧痕残り評価を行った。すなわち、評価1と同様の手順で評価用積層体26を作製し(工程(c)~(e))、評価用積層体26のプリント配線板20p上に半導体チップ22を実装し(工程(f))、はんだリフローを行い(工程(g))、その後、175℃、8MPaで圧縮成型(モールド)を行って(工程(h))、圧痕残り評価用積層体28とした。この圧痕残り評価用積層体28を静置した状態で剥離液(10重量%水酸化ナトリウム溶液)に浸漬させて(工程(i))、プリント配線板20pから第二の基材シート12’(ステンレス鋼板)を剥離した(工程(j))。その後、プリント配線板20pに残る圧痕を顕微鏡観察し、以下の基準で格付け評価した。結果は表3に示されるとおりであった。
‐評価A:圧痕深さが5μm未満であった。
‐評価B:圧痕深さが5μm以上10μm以下であった。この程度の圧痕深さは後工程に影響はしないが、外観が良くない。
‐評価不能:18時間浸漬後においてもステンレス鋼板が剥離しないため、圧痕残りを評価できなかった。
印刷イメージが彫り込まれていない版(シリンダー)を用いて、可溶性粘着層をベタ塗り形成したこと以外は例1と同様にして、粘着シートの作製並びに評価1-1及び2を行った。結果は表3に示されるとおりであった。
Claims (19)
- 基材シートと、該基材シートの少なくとも一方の面に島状又はストライプ状のパターンで設けられた可溶性粘着層とを備えた粘着シートであって、
前記パターンが島状である場合には、該島状のパターンを構成する個々の粘着性領域の外接円の直径が0.1mm以上10mm以下であり、前記パターンがストライプ状である場合には、該ストライプ状のパターンを構成する個々の粘着性領域のストライプ幅が0.1mm以上10mm以下である、粘着シート。 - 前記可溶性粘着層が溶液可溶型樹脂を含む、請求項1に記載の粘着シート。
- 前記溶液可溶型樹脂がアルカリ可溶型樹脂である、請求項2に記載の粘着シート。
- 前記アルカリ可溶型樹脂が、カルボキシル基及びフェノール性水酸基の少なくとも一方を含有するポリマーを含む、請求項3に記載の粘着シート。
- 前記可溶性粘着層の厚さが0.5μm以上50μm以下である、請求項1~4のいずれか一項に記載の粘着シート。
- 前記可溶性粘着層の厚さが3.0μm以上10μm未満である、請求項5に記載の粘着シート。
- 前記可溶性粘着層が前記島状のパターンである、請求項1~6のいずれか一項に記載の粘着シート。
- 前記島状のパターンがドットパターンである、請求項1~7のいずれか一項に記載の粘着シート。
- 前記ドットパターンのドット径が0.7mm以下であり、かつ、前記可溶性粘着層の厚さが1.0μm以上7.0μm以下である、請求項8に記載の粘着シート。
- 前記ドットパターンのピッチ円直径(PCD)が0.45mm以上3.0mm以下である、請求項8又は9に記載の粘着シート。
- 前記粘着性領域の外接円の中心間の間隔が、前記外接円の直径の平均値よりも大きく、かつ、0.1mm以上20mm以下である、請求項1~10のいずれか一項に記載の粘着シート。
- 前記島状のパターンが、全体として、多角形、円、円環状、帯状又は格子状の模様をもたらす1又は複数個のクラスターで構成されており、前記クラスターの各々が、3つ以上の前記粘着性領域の集合体で構成される、請求項1~11のいずれか一項に記載の粘着シート。
- 前記基材シートの前記可溶性粘着層が設けられた面の総面積に対する、前記粘着性領域の割合が3~90面積%である、請求項1~12のいずれか一項に記載の粘着シート。
- 前記基材シートが、ポリエチレンテレフタレート(PET)及びポリエチレン(PE)の少なくとも一方の樹脂で構成される、請求項1~13のいずれか一項に記載の粘着シート。
- 前記基材シートが、金属、ガラス、ガラスエポキシ樹脂、ポリイミド樹脂、及びフェノール樹脂からなる群から選択される少なくとも1種で構成される、請求項1~13のいずれか一項に記載の粘着シート。
- 前記基材シートが、厚さ方向に貫通孔を有する、請求項15に記載の粘着シート。
- 前記可溶性粘着層上に積層された保護フィルムをさらに備える、請求項1~14のいずれか一項に記載の粘着シート。
- 前記保護フィルムが、ポリエチレンテレフタレート(PET)及びポリエチレン(PE)の少なくとも一方の樹脂で構成される、請求項17に記載の粘着シート。
- 請求項1~18のいずれか一項に記載の粘着シートが貼り付けられた被着体から前記粘着シート又は前記基材シートを剥離する方法であって、
前記可溶性粘着層を溶解可能なアルコール含有溶液を、前記可溶性粘着層の島状又はストライプ状のパターンの隙間に浸入させて、前記可溶性粘着層を溶解又は軟化させる工程と、
前記可溶性粘着層が溶解又は軟化された状態で、前記粘着シート又は前記基材シートを前記被着体から剥離する工程と、
を含む、方法。
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